Process for the production of aliphatic isocyanates

ABSTRACT

The present invention is an aliphatic or cycloaliphatic isocyanate obtained form a process comprising the steps of reacting an aliphatic or cycloaliphatic primary amine, with phosgene in the presence of an inert solvent, wherein the initial reaction temperature is between 100 and 130° C. and the temperature is subsequently ramped to 150 to 180° C. during the course of the reaction, the solvent to amine weight ratio is 95:5 to 80:20, the total reaction pressure is maintained between 50 and 350 psig and the amine is rapidly dispersed in the phosgene through injection in a region of high efficiency mixing.

REFERENCE TO RELATED APPLICATIONS

This present application is a continuation application of U.S.application Ser. No. 12/775,715, filed on May 7, 2010, now allowed,which claims priority from U.S. Application No. 61/175,878, filed May 6,2009; each application is incorporated herein, in its entirety, byreference.

FIELD OF THE INVENTION

This invention relates to an aliphatic or cycloaliphatic isocyanateobtained from a process comprising the reacting of an aliphaticpolyamine or its hydrochloride or carbonate with phosgene.

BACKGROUND OF THE INVENTION

Processes to prepare isocyanates by reacting primary amines withphosgene in an inert solvent are known. When the primary amines arearomatic amines, the aromatic amine can be converted with comparativeease to a high purity aromatic isocyanate by contacting the phosgenedirectly with the aromatic amine in a solvent. In the case of aliphaticamines, the overall reaction with phosgene is relatively slow incomparison, thus undesirable chloroderivative by-products are oftenformed.

For these reasons, the production of aliphatic isocyanates is usuallyaccomplished in one of two ways. The first method, known as the saltmethod, involves converting the amine to the hydrochloride or thecarbonate. The resulting salt is transformed into the isocyanate bypassing phosgene through a solvent/hydrochloride slurry at elevatedtemperatures. The second method, known as cold-hot base approach,comprises adding the free amine to excess phosgene, preferably condensedin an inert solvent at low temperatures. The resulting slurry is heatedwhile more phosgene is passed through to complete the reaction.Aliphatic diisocyanates have been manufactured using both methods attemperatures ranging from 130 to 175° C. in a variety of inert solvents.At these temperatures, considerable amounts of chloromonoisocyanates arenoted to form. Unfortunately, the boiling points of the desireddiisocyanates and the chloride impurity derived from them are oftenfound to be quite close, thus rendering separation by distillationdifficult.

When aliphatic isocyanates containing the chlorinated impurity are usedto prepare polyurethane polymers, the chlorinated impurity is known toadversely affect the desired urethane forming reaction. Consequently, alarge amount of work has been compiled detailing process options toreduce the chlorinated impurities obtained during the phosgenation step.GB 1086782 describes a process for the phosgenation of aliphatic amines,or their hydrochloride equivalents, at temperatures of 120 to 180° C. ina weight ration of solvent/amine of 18:1 to 30:1. GB 1050555 discloses aprocess for preparing an organic isocyanate via phosgenation of aprimary amine hydrochloride containing a surface active substance in aninert solvent. JP55-88451A describes the use of a continuous hightemperature phosgenation process. U.S. Pat. No. 2,642,449 discloses aprocess utilizing phosgene injected into the reaction mixture atelevated pressure.

Even when the desired reactions dominate, additional problems areincurred due to the inherent reactivity of aliphatic amines. When eitherthe salt or cold-hot base process is employed, a carbamoyl chloride isformed as an intermediate. The carbamoyl chloride is then subjected todehydrochlorination so that the aliphatic polyisocyanate is prepared.The dehydrochlorination of the carbamoyl chloride into thepolyisocyanate takes place at a low reaction velocity and in general,requires a high reaction temperature of at least 120° C., usually 130°C. or higher. When the polyisocyanate so formed is exposed to heat for along time, the polyisocyanate tends to become tarry, resulting in areduction in the production yield. Further, hydrochloric acid gas whichhas been formed as a result of decomposition of the carbamoyl chloridereacts the resultant polyisocyanate, whereby the carbamoyl chloride isformed again. The carbamoyl chloride becomes tarry at a far higher ratethan the polyisocyanate, so that the yield is reduced further.

The processes of the prior art, however, have been largely ineffectivewhen used with amines that have a high degree of symmetry orcrystallinity, and isomeric mixtures thereof. Amines of this typegenerally yield products having high levels of oligomeric and/orintractable content during the phosgenation reaction.

The prior processes have also been cost ineffective in that they requirelarge amounts of solvent, thus incurring extensive distillation andrecycling costs. As a result, the conventional processes are notamenable to the commercial production of isocyanates directly fromcrystalline or ordered amines.

It is an object of the present invention to provide an economicalprocess for preparing an aliphatic or cycloaliphatic isocyanate, morespecifically isocyanates based isomeric mixtures containing high levelsof a symmetrical or crystalline isomer, in high yields by thephosgenation process.

SUMMARY OF THE INVENTION

In one embodiment, the invention is an aliphatic or cycloaliphaticisocyanate obtained from a process comprising:

-   -   reacting an aliphatic or cycloaliphatic primary amine, or the        hydrochloride or carbonate salt thereof, with phosgene in the        presence of an inert solvent wherein the initial reaction        temperature is between 100 and 130° C. and within 60 minutes of        reaching said reaction temperature,    -   subsequently increasing the temperature to 150 to 180° C. during        the course of the reaction over a time span of about 10 minutes        or less,    -   maintaining the solvent to amine weight ratio from 95:5 to        80:20,    -   maintaining the total reaction pressure between 50 and 350 psig        and    -   dispersing the amine in the phosgene, preferably wherein the        amine is dispersed in the phosgene through injection. Phosgene        is preferably used as a co-solvent.

In another embodiment, the invention is a an aliphatic or cycloaliphaticisocyanate obtained from a process comprising:

-   -   reacting an aliphatic or cycloaliphatic amine, or the        hydrochloride or carbonate salt thereof, with phosgene in the        presence of an inert solvent wherein the reaction is done in two        or more sequential reactors,    -   maintaining reactor temperature from 100 to 130° C.,    -   controlling the solvent to amine weight ration is 95:5 to 80:20,        and the total reactor pressure from 50 to 350 psig and    -   providing a residence time in the first reactor of less than 5        minutes;    -   transferring the product from a first reactor into a second        reactor,    -   maintaining a temperature in the second reactor from 150 to 180        C,    -   controlling a total second reactor pressure from 50 to 350 psig        and    -   providing a residence time in the second reactor of less than 8        hours, preferably wherein the amine is dispersed in the phosgene        through injection.    -   In either embodiment, it is preferred that the aliphatic or        cycloaliphatic amine is composed of an isomeric mixture of        amines, such as 1,3-, 1, 4-bis(aminomethyl)cyclohexane or an        isomeric mixture thereof.    -   The aliphatic polyamine can be selected from the group        consisting of xylylenediamine, hexamethylenediamine,        trimethylhexamethylenediamine, 1,6,11-triaminoundecane,        bis(aminoethyl)cyclohexane, 1,4-diaminocyclohexane,        1,4-bis(aminoethyl)benzene, m-tetramethylxylylenediamine,        p-tetramethylxylylenediamine, 2,4,6-tri(aminomethyl)cyclohexane,        isophoronediamine, bis(aminocyclohexyl)methane,        2,2-bis(aminocyclohexyl)propane, bis(aminomethyl)cyclohexane and        bis(aminomethyl)norbornene.

The reaction is preferably conducted in an inert liquid medium having aboiling point of 90° C. or higher, preferably a solvent having a donornumber greater than 7, especially an organic solvent.

Optionally, either the hydrochloride or carbonate salt of the primaryamine may be used.

When phosgene is used as a co-solvent, increased amine concentrationscan be used, thereby substantially increasing the yield of the desiredisocyanate without incurring the substantial volume requirements of theprocesses of the prior art.

According to the present invention, an aliphatic or cycloaliphaticisocyanate having extremely low impurity contents can efficiently beobtained in high yield, thereby rendering post treatment steps, such asextensive distillation, unnecessary.

DETAILED DESCRIPTION

This present invention relates to a process for preparing an aliphaticpolyisocyanate by reacting an aliphatic polyamine or its hydrochlorideor carbonate with phosgene. It has surprisingly been found that in thecase of symmetrical or crystalline amines, such as1,4-bis(aminomethyl)cyclohexane and isomeric mixtures thereof, that lowinitial reaction temperatures are not advantageous and are, moreimportant, a hindrance to high-yield reactions. Specifically, reactionof bis(aminomethyl)cyclohexanes in dichlorobenzene with phosgene atinitial temperature less than about 80 C produces the normal reactionmixture slurry. However, in heating this reaction mixture to highertemperatures in the second phosgenation stage, the amine hydrochloridesalts agglomerate into an intractable mass. In addition reaction timesare elongated (greater than 10 hours) and overall yields to thebis(isocyanatomethyl)cyclohexane product are less than 75%.

The process of the present invention solves the above-noted problems.According to the present process, phosgene is reacted at increasedtemperature and pressure to increase the rate of formation of acarbamoyl chloride from a corresponding polyamine and at the same time,the reaction temperature is ramped from the initial 100-130 C to 150-180C, to accelerate the formation of the carbamoyl chloride withoutexposing the resultant product to elevated temperatures for prolongedtime periods, whereby the aliphatic polyisocyanate is prepared with theequilibrium always biased toward the polyisocyanate side. This processeffectively decreases byproduct formation derived from reaction ofcarbamoyl chloride during the phosgenation reaction and moreover,increases the rate of formation of the aliphatic polyisocyanate. Thismakes it possible to suppress the conversion of the polyisocyanate intotar and hence obtain the product at a relatively high yield.

The current invention focuses on processes in which the intrinsicphosgene/amine ratio is maintained at high levels during thephosgenation step due to the very slow dissociation rate of said aminehydrochloride. The very high phosgene/amine ratio, in turn, minimizesby-products and thereby leads to high reaction yields. This modificationeffectively eliminates the additional process step of converting theamine to the hydrochloride salt. It also serves to advantageously reducethe overall reaction cycle time.

It has also been found that initial reaction temperatures of from 100 toabout 130 C in a first stage, followed by an increased temperatures inthe second stage, e.g. 150 to 180 C, of the phosgenation effectivelyprevents agglomeration of the initial amine hydrochloride salts. Inaddition, the increased initial reaction temperatures ultimatelydecreases the reaction times to less than 8 hours and substantiallyimproved yields to over 80%. Preferably the residence time is reduced toless than 5 hours. More preferably the residence time is reduced to lessthan 3 hours. Most preferably the residence time is less than 2 hours.

For the phosgenation of 1,4-bis(aminomethyl)cyclohexane, initialelevated temperature mixture and reaction of the amine solution with thephosgene solution provides substantial advantage in consideration ofcommercial processes for the production ofbis(isocyanatomethyl)cyclohexane mixtures.

It has been discovered that high efficiency mixing can effectivelydistribute the amine solution into the reaction mixture. High efficiencymixing is also necessary to obtain high yields and obtaining a reducedresidence time. High efficiency mixing is described in the art, see forexample Gary B. Tatterson, “Fluid Mixing and Gas Dispersion in AgitatedTanks,” McGraw Hill: New York, N.Y., 1991, the disclosure of which isincorporated herein by reference. High efficiency mixing typicallyrequires very high agitation, >10 hp/1000 gal.

The term “aliphatic or cycloaliphatic polyamine” as used herein includesbifunctional or higher organic amines having an alkane moeity with theamino group bonded thereto. Examples of such compounds include linearaliphatic polyamines such as pentamethylenediamine,hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine,2,4,4-trimethylhexamethylenediamine, octamethylenediamine,1,6,11-triaminoundecane and nonamethylenediamine; cyclic polyamines suchas bis(aminomethyl)cyclohexane, bis(aminoethyl)cyclohexane,1,4-diaminocyclohexane, 1,4-bis(aminoethyl)benzene,m-tetramethylxylylenediamine, p-tetraemethylxylylenediamine,2,4,6-tri(aminomethyl)cyclohexane, isophoronediamine,bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane,m-xylylenediamine, p-xylylenediamine, o-xylylenediamine, and mixtures oftwo or more isomers thereof at desired ratios andbis(aminomethyl)norbornene; and amino acid polyamines such as methyllysinate and aminoethyl lysinate.

The present invention is best suited for the production of symmetricalor crystalline isomers, and isomeric mixtures thereof. In the process ofthis invention, these aliphatic polyamines are also usable in the formof hydrochlorides or carbonates. Isocyanates obtained from thesealiphatic polyamines or the salts thereof will be called “aliphaticpolyisocyanates”.

The process of the present invention has a primary feature in thatphosgene is reacted with an aliphatic polyamine or a salt thereof mixedin a liquid medium at a temperature of 100 to 130° C. and the rampingthe temperature to approximately 150 to 180° C., in other words, thereaction is conducted while steadily increasing the temperature.

In the present invention, the solvent is employed to smoothly mix, stirand transfer the raw materials and the reaction mixture so that thealiphatic polyisocyanate can be prepared with ease. The final reactiontemperature can be above 180° C., e.g. up to the degradation temperatureof the isocyanate.

Total reactor pressure is the pressure above the liquid level in thereactor that is comprised of the partial pressures of the reactorcomponents including HCl (generated during the reaction), phosgene,solvent, diisocyanate, and reaction by-products. The total reactionpressure is thus primarily a function of reaction mixture compositionand temperature. Preferably the total reaction pressure of the presentinvention is from 50 to 350 psig. Pressures below 50 psig do not allowthe use of high temperatures as phosgene concentrations adequate forreaction can not be achieved. Although operational pressures may be ashigh 350 psig, total reactor pressures in excess of 350 psig may be usedwithout detrimental effects on the reaction; however, excessively highpressures become increasing cost prohibitive.

Solvents used in the process of the present invention are “inert liquidmedium” which means an organic solvent which is liquid at roomtemperature and does not react with materials in the reaction systemsuch as the aliphatic polyamine, the aliphatic polyisocyanate, phosgene,and hydrochloric acid. Preferably the solvents have a donor (DN) valueof less than 7 as defined by Gutman (V. Gutman, “Coordination Chemistryin Non-Aqueous Solvents,” Springer, Wien: New York, 1968).

Specific examples of the inert liquid medium include hydrocarbons suchas benzene, toluene, mixed xylenes, o-xylene, m-xylene, p-xylene,cumene, 2,2,5-trimethylhexane, decane and ethylcyclohexane; halogenatedhydrocarbons such as chlorobenzene, o-dichlorobenzene,m-dichlorobenzene, p-dichlorobenzene, 1,2,3-trichlorobenzene,1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene and o-dibromobenzene;nitrogen-containing compounds such as nitrobenzene,N,N-dimethylformamide, N,N-dimethylacetamide andN,N-dimethylimidazolidinone; ethers such as dibutyl ether, ethyleneglycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycoldimethyl ether, diethylene glycol diethyl ether, anisole, phenetole,methoxytoluene, benzyl ether and diphenyl ether; ketones such asheptanone and diisobutyl ketone; and esters such as amyl formate, n-amylacetate, isoamyl acetate, methylisoamyl acetate, n-butyl acetate,isobutyl acetate, 2-ethylbutyl acetate, methoxybutyl acetate,ethoxyethyl acetate, methoxyethyl acetate, methoxypropyl acetate, ethylacetate, hexyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate,methylcyclohexyl acetate, benzyl acetate, phenyl acetate, methylCarbitol acetate, ethylene glycol diacetate, ethyl propionate, n-butylpropionate, isoamyl propionate, ethyl butyrate, butyl butyrate, isoamylbutyrate, butyl stearate, butyl lactate, amyl lactate, dimethylphthalate, methyl benzoate and ethyl benzoate. Among these, media whichare liquid under normal pressure at an appropriate reaction temperatureof 90° C. or higher are preferred in view of the economy of reactionfacilities. Of these, esters are particularly preferred because they canact to suppress formation of byproducts called “chlorinated derivatives”in which the isocyanate groups are partly or wholly substituted bychlorine atoms.

These solvents can be used either singly or in combination. From thestandpoint of recovery for reutilization, however, it is preferred touse them singly.

The liquid medium can be used preferably 3-40 times by weight or, morepreferably, 4-20 times by weight of the aliphatic polyamine or its salt.Although an amount smaller than 3 times by weight does not necessarilymean that the reaction will be infeasible, it may become difficult tomix and stir the reaction mixture in some instances. Amounts greaterthan 40 times by weight lead to a deterioration in the volumeefficiency, thereby providing no industrial advantage.

The reaction according to the present invention can be conducted in thefollowing manner: (1) an aliphatic polyamine is employed as a rawmaterial and is initially reacted with phosgene in an inert liquidmedium at 100 to 130 C and then ramping the temperature to about 150 toabout 180° C.; or (2) an aliphatic polyamine is used as a raw materialand, subsequent to formation of its salt by its reaction withhydrochloric acid gas or carbon dioxide gas in the solvent, the salt isreacted with phosgene while ramping the temperature of the mixture ofthe salt and the medium.

In the above-described manner (1), a two-stage reaction is generallycarried out in the solvent. In the first stage, phosgene is chargedwhile maintaining the liquid temperature in a range of 100 to 130° C.,whereby a reaction on a low temperature side is conducted. Although theadvantageous effects can be brought about fully at any temperaturesubstantially higher than 130° C., the decomposition products incurredby prolonged exposure to higher temperatures have a detrimental effecton the overall yield. Further, this low-temperature reaction often givespreferred results when the raw material aliphatic polyamine is alsocharged concomitantly with phosgene at a rate such that the molar ratioof a functional group (amino groups/COCl₂) to the phosgene is between0.06 and 0.2. In the second stage, the temperature is raised from thatin the first stage and reaction at the higher temperature is conducted.The reaction rate tends to become slower at temperatures below 130° C.;the yield tends to drop due to formation of tar at temperatures higherthan 180° C. Temperatures outside the above range are therefore notpreferred.

In the above-described manner (2), the aliphatic polyamine is firstreacted with hydrochloric acid gas or carbon dioxide gas in an inertliquid medium to form the salt of the aliphatic polyamine. The reactiontemperature during this salt-forming reaction is preferably 0 to 60° C.Temperatures lower than 0° C. require an unduly large refrigeratingfacility as in the manner (1) described above, so that the process is nolonger industrially advantageous. Like the low-temperature reaction inthe above-described manner (1), this salt-forming reaction can bringabout preferred results when the raw material aliphatic polyamine isalso charged concomitantly with hydrochloric acid gas at a rate suchthat the molar ratio of a functional group (amino groups/HCl) to thehydrochloric acid gas is between 0.2 and 1.5. Next, after thesolid-liquid mixture is heated, phosgene is reacted. The reactiontemperature is preferably 150 to 180° C., like the high-temperaturereaction in the manner (1).

The present invention may also be carried out by means of a continuousprocess. In a continuous process, the amine dissolved in solvent isreacted with phosgene or phosgene in solvent by high efficiency mixing.The reaction mixture at 100-130° C. then flows through and continues toreact in a tubular reactor or vessel. The reaction mixture is thentransferred by pumping, gravity, or pressure to a second reactor that ismaintained at a higher temperature, e.g., 150-180° C., to completeconversion of the amine hydrochloride to product. Following completeconversion, the process stream is distilled to remove phosgene andsolvent. The crude isocyanate product is then purified by heat treatmentand distillation processes to provide a pure diisocyanate product.

In each manner described above, the solvent is eliminated from thereaction mixture, and the residue is then distilled and purified toobtain the aliphatic polyisocyanate.

The following examples are provided to illustrate the present invention.The examples are not intended to limit the scope of the presentinvention and should not be so interpreted. All percentages are byweight unless otherwise noted.

EXAMPLES Comparative Example 1

In a 1-L Parr reactor, 310 g of 70 w/w % phosgene in 1,2-dichlorobenzeneis heated to 60° C. with 1500 rpm agitation and brought to 350 psig withnitrogen. In a separate vessel, 390 g of 5 w/w %bis(aminomethyl)cyclohexane in 1,2-dichlorobenzene is heated to 60° C.and brought to 462.5 psig with nitrogen. The amine solution istransferred to the agitated phosgene solution through a sub-surfacenozzle. The resulting mixture is held at 60° C. and 350 psig for 5minutes at 1500 rpm, then agitation is reduced to 750 rpm and thereaction temperature is increased to 160° C. When the reaction mixturereaches approximately 80° C., solids agglomerate requiring agitation tobe terminated. As the reaction mixture approaches 160° C., normalagitation (750 rpm) is resumed. After 11 hours at 160° C., the reactionis complete as indicated by the disappearance of visible solids.

Following solvent removal, 22 g of liquid are recovered, along with 3 gsolids. The liquid is analyzed and determined to be 71 w/w %bis(isocyanatomethyl)cyclohexane (by Gas Chromatograph) and 38.9% NCO.

Example 1

A reaction is conducted in the same manner as in the comparative example1, except the initial temperature of the phosgene solution and of theamine solution is 130° C. This mixture is held at 130° C. for 5 minutesat 1500 rpm, then agitation is reduced to 750 rpm and the reactiontemperature is increased to 160° C. No agglomeration occurs, andagitation is unimpeded. The reaction is complete after 8 hours.

After solvent removal, 23 g of liquid are recovered, along with 3 gsolids. The liquid is analyzed and determined to be 80 w/w %bis(isocyanatomethyl)cyclohexane (by Gas Chromatorgaph) and 40% NCO.

Initial amine concentration, w/w %:  3-20 Ratio of phosgene to amineequivalent:  4-16 Initial phosgene concentration, w/w %: 35-90 Solvents:1,2-dichlorobenzene, chlorobenzene, other aromatic solvents Temperature,° C. 120-200 Pressure, psig  50-400 Reaction time, hrs  2-20

Other embodiments of the invention will be apparent to those skilled inthe art from a consideration of this specification or practice of theinvention disclosed herein. It is intended that the specification andexamples be considered as exemplary only, with the true scope and spiritof the invention being indicated by the following claims.

What is claimed is:
 1. A cycloaliphatic isocyanate containing liquidcomposition obtained from a process comprising: reacting acycloaliphatic primary amine, or the hydrochloride or carbonate saltthereof, with phosgene in the presence of an inert solvent wherein theinitial reaction temperature is between 100 and 130° C. and within 60minutes of reaching said reaction temperature, subsequently increasingthe temperature to 150 to 180° C. during the course of the reaction overa time span of about 10 minutes or less, maintaining the solvent toamine weight ratio from 95:5 to 80:20, maintaining the total reactionpressure between 50 and 350 psig and dispersing the amine in thephosgene; wherein the cycloaliphatic amine is selected from the groupconsisting of 1,3-bis(aminoethyl)cyclohexane,1,4-bis(aminomethyl)cyclohexane, bis(aminoethyl)cyclohexane,1,4-diaminocyclohexane, 2,4,6-tri(aminomethyl)cyclohexane,isophoronediamine, bis(aminocyclohexyl)methane,2,2-bis(aminomethyl)propane, bis(aminomethy)cyclohexane,bis(aminomethyl)norbornene, and isomeric mixtures thereof; and whereinthe cycloaliphatic isocyanate containing liquid composition comprises,following solvent removal and in the absence of any further separationsteps, 80 w/w % or greater, but less than 100 w/w % of cycloaliphaticisocyanate, and balance unreacted phosgene and chlorinated byproducts.2. The cycloaliphatic isocyanate of claim 1 wherein the amine isdispersed in the phosgene through injection.
 3. The cycloaliphaticisocyanate of claim 1 wherein phosgene is used as a co-solvent.
 4. Acycloaliphatic isocyanate containing liquid composition obtained from aprocess comprising: reacting an aliphatic or cycloaliphatic amine, orthe hydrochloride or carbonate salt thereof, with phosgene in thepresence of an inert solvent wherein the reaction is done in two or moresequential reactors, maintaining reactor temperature from 100 to 130°C., controlling the solvent to amine weight ration is 95:5 to 80:20, andthe total reactor pressure from 50 to 350 psig and providing a residencetime in the first reactor of less than 5 minutes; transferring theproduct from a first reactor into a second reactor, maintaining atemperature in the second reactor from 150 to 180 C, controlling a totalsecond reactor pressure from 50 to 350 psig and providing a residencetime in the second reactor of less than 8 hours; wherein thecycloaliphatic amine is selected from the group consisting of1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane,bis(aminoethyl)cyclohexane,1,4-diaminocyclohexane,2,4,6-tri(aminomethyl)cyclohexane, isophoronediamine,bis(aminocyclohexyl)methane, 2,2-bis (aminocyclohexyl)propane,bis(aminomethyl)cyclohexane, bis(aminomethyl)norbornene, and isomericmixtures thereof; and wherein the cycloaliphatic isocyanete containingliquid composition comprises, following solvent removal and in theabsence of any further seperation steps, 80 w/w % or greater, but lessthan 100 w/w % of cycloaliphatic isocyanate, and balance unreactedphosgene and chlorinated byproducts.
 5. The cycloaliphatic isocyanate ofclaim 4, wherein the amine is dispersed in the phosgene throughinjection.
 6. The cycloaliphatic isocyanate of claim 1, wherein thealiphatic or cycloaliphatic amine is composed of an isomeric mixture ofamines.
 7. The cycloaliphatic isocyanate of claim 1, wherein thecycloalipahtic amine is selected from the group consisting of1,3-bis(aminomethyl)cyclohexane, 1,4-bis (aminomethyl)cyclohexane or anisomeric mixture thereof.
 8. The cycloaliphatic isocyanate according toclaim 1, wherein the cycloaliphatic amine is selected from the groupconsisting of bis(aminoethyl)cyclohexane,1,4-diaminocyclohexane,2,4,6-tri(aminomethyl)cyclohexane, isophoronediamine,bis(aminocyclohexyl)methane, 2,2-bis(aminocyclohexyl)propane,bis(aminomethyl)cyclohexane and bis(aminomethyl)norbornene.
 9. Thecycloaliphatic isocyanate according to claim 1, wherein the reaction isconducted in an inert liquid medium having a boiling point of 90° C. orhigher.
 10. The cycloaliphatic isocyanate according to claim 1, whereinthe inert liquid medium is an organic solvent having a donor numbergreater than 7.